Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
  • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
  • C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
  • C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/85—Coating or impregnation with inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B29/00—Other details of coke ovens
  • C10B29/06—Preventing or repairing leakages of the brickwork
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B43/00—Preventing or removing incrustations
  • C10B43/02—Removing incrustations

Definitions

• the present invention relates to a coating agent for a coke oven carbonization chamber and a method of applying the same, and relates to a technique for coating the surface of a refractory that is exposed to high temperatures and is subject to friction, thereby improving the durability of the refractory.
• Japanese Patent Publication No. WO 95/3314/18 published the R 2 O (Na 2 O or K 2 ⁇ ) and Si as basic components of glaze.
• 0 consists of two Metropolitan, preferably those this was added one or two L i 2 O and B 2 0 3, discloses a carbon attachment prevention glaze melting point of glaze is less than 900 ° C I have.
• Kei acid sodium is a 2-3-8 35.0 to 50.0%, lithium hydroxide 1.0 1.0 to 10.0% of sodium borate, R-Si (OH) 2ONa (where R is an alkyl group having from 12 to 12 carbon atoms).
• a treated material consisting of 1.0 to 100% and water and having a viscosity of 100 cps (20 ° C) or less is sprayed onto the surface of a refractory material with a surface temperature of 10 to 500 to 1000 ° C using a spray nozzle.
• 0.05-4.0 kg / ra :
• Refractory material surface By coating, a molten coating layer is formed on the refractory material surface, and the subsequent temperature rise causes the reaction between the refractory material surface layer and the molten coating layer and the evaporation of sodium, S i 0 2 purity is high, in which the surface is as smooth intensity to obtain a high processing layer.
• the inventors of the present invention have been enthusiastically researching to develop a further excellent coating material, and have developed a coating agent for a coke oven carbonization chamber having more excellent characteristics than the above-mentioned conventional technology.
• An object of the present invention is to provide an excellent coking oven carbonization chamber coating agent having a composition different from that of the prior art.
• the present invention is a coating agent for a coking oven carbonization chamber characterized by taking the following technical means. That is, in the present invention, the composition of the glaze layer
• a coating agent for a coke oven carbonization chamber characterized in that it contains one or more of the following.
• the glaze layer of the present invention contains an alkali silicate as a main component.
• Alkali silicates which form glass are usually those having an oxide equivalent of Sio 2 : 18 to 70% by weight, Na 2 O and / or K 2 ⁇ : 10 to 60% by weight. In this case, too, a material with such a component is used. Since the coating agent of the present invention is used by spraying it on a high-temperature brick surface as described below, it is preferable to use water glass.
• ⁇ 2 0 3 is a preferable characteristics when containing 0.5 to 10 wt%.
• the method for applying the coating agent of the coke oven carbonization chamber of the present invention is as follows. In other words, an aqueous solution or slurry of the coating agent in the coke oven carbonization chamber is prepared, sprayed on the surface of a high-temperature refractory brick at a temperature of 500 to 1400 ° C, and then maintained at a temperature of 900 ° C or more for 30 minutes or more. This is a method of applying a coating agent for the coking oven.
• the coke oven carbonization chamber coating agent of the present invention can provide a long-term glass coating by adding one or more of P, Ba, Sr, and Fe to sodium silicate and / or potassium silicate.
• a chemical that acts on carbon on the brick surface that adversely affects stability and removes it by oxidation, forming a glaze layer with high melting point, high strength, and high smoothness.
• trace amounts of Ca, Mg and A1 can be added to improve the brittleness of glass.
• compounds of P, Ba, Sr, Fe, Ca, Mg, and A1 in which the pH of sodium silicate is stable in an alkaline region, are used.
• Sodium silicate which is generally known as a binder and a constituent of the glass skeleton, acts as a flux to enhance the initial spreadability of P, Ba, Sr, and the like.
• the P 2 0 5 source, using a phosphate cation component is sodium and Bruno or potassium.
• a tertiary phosphate, a secondary phosphate, a metaphosphate, a pyrophosphate, a polymerized phosphate (a tripolyphosphate, a hexametaphosphate, etc.) may be used alone or in combination.
• the melting point of these phosphate itself is quite about 630 to 1,340 D C wide, but only a small amount added to the water glass system, the melting point of the phosphate itself to be added irrespective of water glass-based Decrease the melting point. However, a large amount of addition increases the melting point.
• P 2 o 5 is the melting point of the glaze exceeds 14 wt% significantly adhesion rise to glaze the brick is reduced. In addition, the stability of the product is impaired by increasing the proportion of phosphate in the blended raw materials. On the other hand, there is no effect as a flux when P 2 0 5 is less than 1 wt%, uniform glaze is not formed. Thus, the 1-14% by weight P 2 0 5 basis. More preferably, it is 2 to 8% by weight.
• P When P is added in a certain range, it is extremely effective in smoothing the coating surface at the beginning of coating, and at the same time, it resists high-temperature chemicals that come into contact with the glass surface (interface), such as tar vapor and H 2 S gas. The force increases and the life of the glass increases. In addition, over time, A phosphate-based glass with a high melting point is formed on the surface of the coating layer to eliminate the adhesiveness of the coating layer. P can increase the life of glass from a mechanical and chemical standpoint.
• B a is in a high temperature air atmosphere varies B a O (B a 0 2 ).
• B a O (B a O 2 ) is rich in oxidation catalytic power, and oxidizes (burns) the carbon permeating the brick outer surface by the following formula to remove it.
• B a O + lZ20 2 B a 0 2 (oxidation when the furnace door is opened)
• B a O is combined with the brick substrate S i 0 2
• the oxidation catalytic power gradually decreases, but the carbon No coating layer is formed.
• B a O itself, melting point as high as 1923 ° C, the suppressing film reduction melting point lowering of S i 0 2.
• BaO source sulfates, oxides, hydroxides, carbonates, chlorides and nitrates can be used.
• the amount of Ba added is 0.5 to 25% by weight in terms of BaO.
• BaO is used to increase the melting point of the glaze layer and increase the strength of the glaze layer.
• the BaO content exceeds 25% by weight, unmelted substances are contained in the glaze layer.
• the surface of the glaze layer is not smooth due to the scattered and uniform molten layer.
• the content is less than 0.5% by weight, the effect of adjusting the melting point is not exhibited, and the effect of eliminating carbon is insufficient. Most preferably, it is 3 to 15% by weight.
• any one of a hydroxide, a carbonate, a chloride, and a nitrate, or a mixture thereof is used.
• Sr finally changes to SrO at high temperatures, showing a high melting point of 2430 ° C and at the same time contributing to an improvement in the strength of the glass layer.
• Various S r compounds of will vary to a high temperature CO gas and glowing Kotasu almost S r C0 3 under conditions in contact (mp 1497 ° C), it changed to S r O refractory at 1350 ° C.
• SrO has a very high melting point, which increases the melting point of the glass layer and lowers the wettability.
• SrO contributes to an increase in the melting point and strength of the glaze layer, similar to BaO. If the content of SrO is less than 0.5% by weight, the effect of increasing the melting point is poor. Is not smooth. Therefore, it was set to 0.5 to 25% by weight. A more preferable value is 3 to 15% by weight for the same reason.
• the Fe source may be a complex salt of potassium ferrosyanide, potassium ferricyanide, sodium ferrosyanide, or a solution of ferrous phosphate, ferric phosphate, iron chloride, iron nitrate, iron sulfate, or a particle having a particle diameter of 200 ⁇ or less.
• e 3 0 4 F e 2 0 3, F e OOH is used.
• tartaric acid, cunic acid, thioglycolic acid, thiocyanic acid, sulfosalicylic acid, chelated iron composed of EDTA and iron, or iron iron ammonium obtained by adding ammonia to these can be used.
• F e compound generates F e O, F e 3 ⁇ 4, ultrafine particles of F e 2 0 3 at a high temperature, shows a catalytic function You.
• Fe compounds have long been used as coal combustion promoters. The following reactions gasify carbon, and the Fe components are oxidized when exposed to air.
• the amount of Fe added was 0.5 to 20% by weight in terms of Fe 2 O 3 . If less than 0.5% by weight, no effect of adjusting the melting point can be seen, and if more than 20% by weight, unmelted substances are scattered in the glaze layer as in BaO and SrO, resulting in uniform melting. The smoothness of the glaze layer surface is impaired without forming a layer. Therefore, it is set to 20% by weight or less. A more preferable addition amount is 3 to 15% by weight.
• the above-mentioned additive components P, Ba, Sr, and Fe each independently perform the above-mentioned actions, and when combined with each other, have a synergistic effect on properties. Therefore, carbon-free, durable, and strong It is possible to form a refractory brick coating layer having a large size. Further, boron as in the conventional Kei sodium glass, 0.5 to 10 weight at B 2 0 3 basis. / 0 may be added, and the high-temperature tackiness due to B is improved by the above-mentioned other added components, and an excellent coating layer can be formed.
• the coke oven carbonization chamber coating agent of the present invention is made into an aqueous solution or slurry, sprayed on the surface of a high-temperature refractory brick, and kept at a temperature of 900 ° C or more for 30 minutes or more after spraying. If the temperature is lower than 500 ° C, the oxidation removal reaction of carbon does not proceed, and a high temperature exceeding 00 ° C is not required. After spraying, keep the temperature at 900 ° C or more for 30 minutes or more. If the temperature is less than 900 ° C, it is difficult to obtain an excellent glass layer, and if the holding time is less than 30 minutes, it is insufficient. Preferably, it is 60 minutes or more.
• Figure 1 is a graph showing carbon combustion efficiency.
• FIG. 2 is a schematic cross-sectional view near the surface layer of the brick.
• FIG. 3 is a schematic cross-sectional view near the surface layer of the brick.
• FIG. 4 is a schematic cross-sectional view near the surface layer of the brick.
• FIG. 5 is a schematic cross-sectional view near the surface layer of the brick.
• Conventional coating agents mainly consisted of fluxes (sodium silicate, lithium and boron), all of which had low melting points, and when the coke oven was in operation, had obtained smoothness by dissolving the brick surface. This flux changed thermally and took a long time to reach the melting point of 1430 ° C, and when the amount of coating was large, it conversely caused clogging.
• fluxes sodium silicate, lithium and boron
• the present invention has eliminated or reduced the concentration of components that continue to have the function of lowering the melting point, such as conventional lithium and boron.
• the coating agent containing these components having the function of lowering the melting point has a drawback that the glass formed on the brick surface maintains its tackiness at high temperatures.
• the disadvantage was solved by adding a component that quickly raises the melting point.
• the coating agent of the present invention has the same high adhesiveness at the initial stage of application at high temperatures as in the past, and after several hours, a component which causes an increase in the melting point due to the high concentration of the high melting point component near the application surface.
• Ba, Sr, and phosphates Ca, Mg, and A1 solved the problem.
• FIG. 2 and 3 are schematic cross-sectional views of the vicinity of the surface layer of the brick 1.
• FIG. Carbon 2 is present on the coating surface of brick 1 (the part where the coating solution has penetrated). As shown in FIG. 2, when this coating layer 3 wraps around the carbon 2, as shown in FIG. Eventually, the carbon 2 disappears, and this part becomes the surface peeling part 4, which lowers the adhesive strength of the coating layer 3 itself, and causes the surface peeling of the coating layer 3 when the coatus is extruded. For this reason, the smoothness of the surface is lost, and the carbon firmly adheres and grows from the surface peeling portion 4 as a starting point.
• the oxidation catalytic reaction is applied to quickly eliminate the carbon on the brick surface. That is, at the stage of forming the coating layer 3 shown in FIG. 2, the carbon 2 on the surface of the brick 1 is eliminated, and as shown in FIG. 3, the coating layer 3 integrated with the fine voids 5 on the brick surface is formed. be able to.
• Figure 1 is a graph showing the carbon combustion efficiency of the coating agent of the present invention.
• the coating agent according to the present invention was mixed with coats powder assuming carbon in the coating agent and reacted in an atmosphere of 0.2% oxygen concentration. It measures the change in weight and the calorific value when it is heated. At a heating temperature of 500 ° C to 600 ° C, a decrease in the weight of the carbon and an increase in the calorific value are clearly shown, indicating that there is an effect of eliminating carbon. This is due to the fact that carbon, which is generated at the time of carbonization and penetrates into the fine voids, not only forms a strong coating layer as described above, but also causes a slight carbon adhesion layer to remain on the wall of the carbonization chamber when forming the coating layer. A strong coating layer can be formed, This has great practical value because carbon removal from the carbonization chamber wall during coating can be performed extremely easily.
• the viscosity of the molten layer (before vitrification) immediately after application of the coating agent can be reduced, and smoothness can be improved by improving wettability. it can.
• the viscosity was high, it was difficult to penetrate into the voids 5, and the surface irregularities 7 occurred.In the present invention, however, as shown in FIG. In addition, the coating agent penetrates into the space 5.
• the coating agent of the present invention quickly eliminates carbon by an oxidation catalytic reaction, and forms a glass layer having a higher melting point, higher strength, and smoothness than before.
• the metal phosphate (Mg, Ca, Al, Ba, Fe) is added or the metal phosphate formed by the reaction between the phosphate and the metal at high temperatures is present.
• these metal phosphates do not react with water glass-based glass at high temperatures, exist alone, and have a different melting point from water glass-based glass (water glass, fluxes). As a result, it becomes closer to the surface of the water glass system and forms a thin, strong glass surface with a high melting point. That is, a composition composed of a metal phosphate such as a phosphoric acid Ca-based material has a surface strengthening / modifying effect on water glass-based glass.
• the surface of the applied brick contains limestone due to the penetration of tar and the like generated during carbonization.
• this carbon gradually dissipates and disappears after coating, creating voids in the coating layer and the brick surface, resulting in a reduction in strength and a shortened service life.
• this carbon is oxidized and removed at an early stage, and a film having a higher melting point, higher strength, and smoothness than conventional products is formed.
• the coating agent for the carbonization chamber of the coke oven of the present invention is prepared by adding water to form an aqueous solution or slurry and applying it to the refractory surface inside the coke oven by spraying. You.
• the sprayed coating material vitrifies at high temperatures and forms a strong glass layer. For this reason, the surface temperature of the applied brick needs to be higher than the temperature at which the drug solid content after the aqueous solution or the slurry water evaporates is melted.
• JISK 1 4 0 8 one water glass as defined in (N a 2 O: 17 ⁇ 19 wt%, S i 0 2: 35 ⁇ 38 wt%, water: residual wt%), the two water glass
• Tables 4, 5, and 6 show the oxide equivalents (excluding components that evaporate at high temperatures) of each component of this formulation.
• the aqueous solutions or slurries shown in Tables 1, 2, and 3 were sprayed onto the surface of the sample refractory brick heated to 700 ° C with a bonfire attached to the surface.
• the components of the refractory brick are shown in Table 7.
• the spray amount was 0.1 kg per m 2 of surface area.
• 950 sample refractory brick. C for 60 minutes and cooled naturally. Tests were performed on the hot tack of the generated glaze layer surface, the adhesion between the glaze layer and the brick after cooling, the smoothness of the glaze layer surface, and the hot shock resistance of the glaze layer surface.
• Table 8 also shows the results of a similar test performed on a comparative example (conventional example) showing the composition of the composition.
• Table 9 shows the oxide equivalents (excluding components that evaporate at high temperatures) of the components in the blends in Table 8.
• Test method 2 With the brick kept at 950 ° C, press the glaze layer with a flat iron cylinder for 1 minute, then pull it back. The glaze layer's adhesion resistance to iron was observed and evaluated. If the stickiness is high, the glaze layer will cause stringing, and the more sticky, the longer the stringing.
• the cooled brick was dropped from a height of 2 m and the state was observed.
• Judgment was made by visual observation and finger touch observation of the cooled brick.
• Tables 1 to 9 show that the coating agent for the coke oven carbonization chamber according to the example of the present invention has improved properties and is more durable than the comparative example, but in particular P, Ba, Fe, S
• the coating material with the combined addition of r, A1, and Mg shows extremely excellent properties.
• KSi Kayic acid ream
• NaB Sodium borate
• NaP Trisodium phosphate
• CaP Calcium phosphate
• A1P Aluminum phosphate
• K Fe Potassium ferrosyanide
• the coating agent of the coke oven carbonization chamber of the present invention is configured as described above, it has higher strength, higher impact resistance, superior smoothness, greater durability, and greater durability than conventional coating materials. Long-term protection of refractory bricks has become possible.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Ceramic Engineering (AREA)
• Structural Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Glass Compositions (AREA)
• Furnace Housings, Linings, Walls, And Ceilings (AREA)
• Ceramic Products (AREA)
• Coating By Spraying Or Casting (AREA)

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• 1997
  • 1997-02-28 JP JP9046123A patent/JPH10236891A/ja active Pending
• 1998
  • 1998-02-04 AU AU57800/98A patent/AU724647B2/en not_active Ceased
  • 1998-02-04 WO PCT/JP1998/000466 patent/WO1998038144A1/ja active IP Right Grant
  • 1998-02-04 DE DE69814285T patent/DE69814285T2/de not_active Expired - Fee Related
  • 1998-02-04 CN CN98800212A patent/CN1131187C/zh not_active Expired - Fee Related
  • 1998-02-04 CA CA002249285A patent/CA2249285C/en not_active Expired - Fee Related
  • 1998-02-04 US US09/142,453 patent/US6165923A/en not_active Expired - Fee Related
  • 1998-02-04 EP EP98901509A patent/EP0908428B1/en not_active Expired - Lifetime
  • 1998-02-04 BR BR9805919-0A patent/BR9805919A/pt not_active IP Right Cessation
  • 1998-02-19 ZA ZA981379A patent/ZA981379B/xx unknown
  • 1998-02-20 TW TW087102408A patent/TW362093B/zh not_active IP Right Cessation

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